Process for breaking petroleum emulsions



' kylene radicals for each hydroxyl group,

icon atoms, and in such a manner as lr' atented July 5.3, that!) PRGQESS FQE BREAKWG PEEiitillJEUIt ll lEMllllLSlQN S Melvin Tile Groote, 'ilniyersity City, and Ttiernhard Keiser, liil'elister G Petrolite Corporation, corporation of Delaware roves, \ii/io Md Wilmington, well a ass-ignore to No Drawing. Application June 15, lliiilz, Serial No. tidhldfl 1 Claims.

Another object is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oihsuch as crude petroleum and relatively soft waters or. weak brines. Controlled emulsiflcation and subsequent demulsification under the conditions just mentioned is of significant value in removing impurities, particularly inorgarlic salts, from pipeline oil.

We have discovered that if one oxyalkylates ,glycerol so as to introduce at least three oxyaland if the product 'so obtained is reacted with a polybasic carboxy acid having not over eight carto yield a {fractional ester, due to the presence of at least one free carboxyl radical, one can then esterify' said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which are efficient demulsiflers for crudeoil emulsions.-

The compounds herein described, that are used I as the demulsifier of our process, may be produced in any suitable manner, but are usually manufactured by following one 'of two general procedures. In one of said procedures the owalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic-material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described, and momentarily indicatedby the formula (R1(OH) m. Generlcally, the alcoholic body herein contemplated may beconsidered a member of the class in which m may vary from 1 to 10, although the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react analcohol of the formula type R1(0H)m with a polybasic acid so as tov produce an intermediate product, and then react said intermediate product or fractional ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

0 H C 3H50H if treated with an onyallrylatlng agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an oXyethylated glycerol of the following formula type:

( 2E4 )nH aHnOr-(C2HiO)n'H (CaHaO) NH V in which the value of a may vary from 3 to 10 and all the values of it need not be identical. If a polybasic carboxy acid be indicated by the formula:

ooon e-coon coon then the acyclic reaction product of one mole of oxyethylated glycerol and one mole of a polybasic carboxy acid may be indicated by the following f ormula:

(ciulowoocmoo0H),.-

in which n" has the value of one or two. Similarly, if two moles of the polybasic acid be used, then the compound may be indicated by the following formula:

Likewise, if three moles of a polybasic acid are employed, the compound may be indicated by the following formula:

(osmou ooc'moo 011 C3H5Oa(C2H4O)n'OOCRKJOOH)I." (cimowoocmooomw 'viously described'in a generic sense as R1(OH) m,

then obviously, one may obtain, a material of the type indicated by the following formula:

in whichxis 0,1or2,yis0,1 or2, andzis 1,2or 3, and :c' is 0 or 1, and y is 1 or 2.

It has been previously stated that compounds I of the type herein contemplated may be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene of ethylene glycol.

oxide and glycid, which, although not included, strictly speaking, by' the unitary structure CnHZnO, is included within the meaning of the hereto appended claimsand may be simply considered as a variant of proplyene oxide, i. e., hydroxypropylene oxide. Similarly, wherea carboxylic hydrogen atom appears, it may be replaced by metal, an ammonium radical, or substituted ammonium radical, or by an organic group derived from an alcohol, such as an aliphatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an amide, including a polyamionamide. Thus, the'preceding formula may be rewritten in its broader scope, as follows:

but generally speaking, esterifications can be car- I cerned with materialsof this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esteriflcation products of the monomeric compounds. I In view of what has been said, and in viewof the recognized hydrophile properties of the recurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the maried out at-the lowest feasible temperatures by using one of several procedures. One procedure is'to passan inert dried gas'through the mass to be esterifled, and have present at the same time a least one free hydroxyl,;.or both.

solvents, such as water, alcohol, benzene, di-' chloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane. or the like. This is simply another way of stating that the polymerized product contemplated must be of the subresinous type, which is commonly referred to as anA resin, or a B resin, as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq.).

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which containneither a free hydroxyl nor a free carboxyl group, andone may also obtain a compound of the type in which there is present at least one free carboxyl, or at The word "polar? has sometimes been used inthe arts in small amountof a catalyst, such as dried HCl gas, a dried sulfonicv acid, or the like. Another and better procedure, in manyinstanqes, is to employ the vapors of a suitable liquid, so as to remove liquid to the reactingvessel.

commonly employedin the arts, and for convenience, reference 'is made; to U. S. Patent No." 2,264,759, dated December 2, 1941, to Paul 0.113 'Jones.

. Referring again tothe last two formulas indi cating the compounds under consideration, it

can'be readily understood thatsuch compounds,

in numerous instances, have the property of polyfunctionality. In view of this fact, where there is at least one residual carboxyl and at least one residual hydroxyl, one would expect that under suitable conditions, instead of obtaining the monomeric compounds indicated, one would in reality obtain a polymer in the sense, for example, that polyethylene glycols represent a polymer derived from a monomer in which the polymer this particular sense to indicate the presence of at least one freehydroxyi group,.or at least one free carboxyl group, or both. in theQcase of the l free 'carboxyl group, the 'carbo xylic-- hydrogen atom may,of course,;be replaced-by any ionizable hydrogen atom equivalent, such, i'or: example, as

a metal, an ammonium radical, a substituted ammonium radical, etc; In atheqheretor appended claims the word polar is used-in this specific senses-f We-areaware that compoundslsimilar to those contemplated in the present instance-may be derived rmm polyhydroxylated compounds having more'than' three hydroxyl'g'roups; Forinstance,

" they'may be' derived from acyclic *diglycerol, triglycerol, tetraglycerol, "mixed polyglycerols, mannitol, s'orbitol, various ihGXltOlSf dulcitol, pentaerythritol, sorbitan, mannitan, dipentaerythritol; monoether,- and other similar compounds. "Such particular-types in which higher The term polymer" is frequently used to indicate the polymerized product has the same identical composition as the' monomer. V polymerization involves'the splitting and loss of water so that the process is essentially self-esteriflcation. Thus, strictly speaking, the polymeric compounds are not absolutely polymers of the monomeric compounds, but since, for all 'practical purposes, they can be so indicated, and since such practice is common in the arts con- In the present instance, however, I

'hydroxylated materiaisare subjected to oxyal- [kylation and then employed in the same manner as oxyalkylated glycerol, is employed in the pres- -ent instance, are not contemplated inthis specific case, although'attentionis directed to the same. j j I l Reference is also made to other oxyalkyiated compounds which may be used as reactants to,

replace oxyalkylated glycerol. or oxyalkylated ethylene glycol, which latter reactant is -described in a co-pending application hereinafter referred to. The reactants thus contemplated include thetype in which there is an amino or amido nitrogenatom, particularly,,when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or 'type of alcoholic bodies for reactants, but is limited, among other tl iings, to the compounds which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, in the present instance,

' one, two, or three, or more, .might be introduced.

As indicated previously, the polyba'sic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic,

malonic, succinic, glutaric, adipic, maleic, and

phthalic. Similarly, one may employ acids such as fumarlc, elutaconic, and various others, such as citric, malic, tartaric, and the like. Theselection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and. also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final prod! not be of a sub-resinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain, large'yields of esterifled product, although polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an-anhydride, sucham hydride is apt to produce the ester with greater "case than the acid itself. For this reason, maleic 'anhydride is particularly adaptable, and also,

everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or the anhydridc has many attractive qualities of maleic anhydride, and this is also true of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, referenceis made to derivatives obtained by oxyethylation,

although, as previously pointed out, other oxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately 15 to 2d oxyethylene groups have been introduced Iinto a single glycerol molecule. This means that approximately five to eight oxyethylene radicals have been introduce'dfor each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11 of German Patent- No. 605,973, dated November 22, 1934, to I. G. Farbenindustrie Akt. Gee). The procedure iii-- dicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

Oxmrarmrrn Gnrcrizox. Example 1 184 pounds of glycerol is mixed with by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relative- 1y small amounts, for instance, about 44 pounds at a time. p The temperature employed is from Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding;

. Oxrrrrrrmren Gin-manor:

Example 3 J The same procedure is followed as in the two previous examples, except thatv the ratio of ethylene oxide to glycerol is increased to 21 to one.

OXYETl-IYLATED GLYCEROL MALEATE Example 1 1 One pound mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated with one pound mole of maleic anhydride and heated at approximately C. for approximately thirty minutes to two hours, with constant stirring, so as to yield a monomaleate.

OXYE'I'HYLATED GLYCEROL MALEATE Example 2 The same procedure is followed as in the pre-.- ceding example, except that two moles of maleic anhydride 'are employed so-as to obtain the dl-. maleate instead of the monomaleate.

OxxErHYLA'rsn GLYCEROL' MALsArE Example 3 The same procedure is followed as in the two preceding examples, except that three moles of malelc anhydrides are employed so as the trimaleate. g

OxYE'mYLA'rED GLYCEROL MAI-BATE Example 4 1 'The same procedure is employed item the preceding examples, except that oxyethylated glycer-. 01 (ratio 1 to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15).

OXYETHYLA'I'ED GLYCEROL Manners Example 5 The same procedure is employed as in the praceding examples, exceptrthat oxyethylated glyto obtain 1 the manufacture of the present compounds, are

water-insoluble esters of trihydric alcohols, char: acterized by being derived from high molal hydroxy acids and also by the fact that there isno residual hydroxyl radical attached to the polyhydrlc alcohol residue; i. e., the compounds are neutral or complete esters, as differentiated from fractional esters. The pplyhydric alcohols employed asreactants for the production of the neutral esters of the high molal hydroxy acids are characterized by the fact that they contain three hydroxyl groups, the commonest example being glycerol. Trihydric alcohols maybe obtained by etherization reactions involving monohydric al cohols and polyhydric alcohols having more than three hydroxyl radicals, as, for example, diglycerol, pentaerythritol, mannitan, sorbitan, etc.

The ethyl ether, 'butyl ether, or other alkoxy derivatives of diglycerol, is an additional illustration of this particular type. Any -trihydric alcohol,

vi. e., any triol, can of course be treated with an alphabeta alkylene oxide, such as ethylene oxide,

nation'of a sulfoaromatic fatty acid. In any event, by employing derivatives of undecylenic acid, or one or more of the various wax acids, naturally-occurring naphthenic acid, ricinoleic acid, diricinoleic acid, or derivatives thereof, as have been enumerated, one can obtain a variety of hydroxylated monocarboxy acids, having at propylene oxide, or the like, so as" to add an al-.

koxy group and still retain a terminal hydroxyl group. The oxyalkylation of glycerol by means of ethylene oxide illustrates this type. It is not intended to include ether alcohols, particularly ether glycerols, in which the ether linkage'occurs more than four times.

The 'trihydric alcohols 0r triols just described are esterified with or converted by any suitable ,means, into water-insoluble esters of high molal hydroxy acidshaving at least 8 carbon atoms and not in excess of 36 carbon atoms. The commonest example of, a. high molal hydroxy acid is ricinoleic acid.

Otherhydroxy fatty acids include hydroxystearic acid, dihydroxystearic acid, diriconoleic acid, aleuritic acid, and the like. Similaracids are obtained in the oxidation of paraflin, petroconverted'into a hydroxy undecanoic acid. Un-' saturated hydroxy acids, such as ricinoleic acid, may be treated in various manners, so as to produce derivatives, for example, chlorinated or brominated ricinoleic acid. Suchmaterials are entirely satisfactory for use as-reactants in the preparation of materials of the kind herein contemplated. Naturally-occurring naphthenic. acids can also be converted into hydroxylated -products by following similar procedure. An unsaturated hydroxy acid, such as ricinoleic acid, can be converted into a hydroxylated arylstearic acid. Such procedure contemplates reactions such as those involving ricinpleic acid, benzene, and aluminum chloride in large excess, or involves the desulfocal acids of the kind described, attention is directed lea'st 11 carbon atoms and not in excess of 36 carbon atoms. Such compounds are the kind herein contemplated as reactants to furnish the alcoholiform hydroxyl.

Hydroxy acids of the kind herein contemplated may also be prepared by the hydrolysis of alphahalogen acids. For instance, alpha-bromocaproic acid, alpha-bromocaprylicacid, alpha-,- -bromocapric acid,al.pha-bromolauric acid, alphabromomyristic acid, alpha-bromopalmitic acid, and the like, can be hydrolyzed waive the corresponding alpha-hydroxy acid. Indeed, a reactive alpha-halogen acid may serve as a functional equivalent of an alpha-hydroxy acid by liberation of hydrochloric acid, instead of water. Such type ofreaction, however, involves numerous difliculties; and thus, it is better to employ a hydroxy acid.

In some instances derivatives of a hydroxylated unsaturated acid are most readily obtained by the, employment of an intermediate in which the a derivative in which an aryl group is introduced.

. Such derivative can then be saponified or bydrolyzed so as to regenerate the hydroxyl'radias to the manufacture of various esters from to the followin United States Patentsz, No.

No. 2,177,407, dated-Oct. 24, 1939, to Hensley.

See also Organic Syntheses, volume X, ,page 88, 1930.

COMPLETED MONOME-RIC DERIVATIVE Example 1 One pound mole of a product of the kind de-' scribed under 'the heading Oxyethylated glycerol maleate, Example. 1 is reacted with one pound mole of triricinolein, preferably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher lboiling range than xylene, and sometimes removal of such solvent might present -a dimculty.

if employed, mightbe permitted to remain in the reacted mass and appear as a constituent or in- 1 gredient of the final product. In any event, our

C.' and time of reaction about 20 hours.

COMPLETED MONOMERIC DER IVATI E Example 2'- pleted monomeric derivative, Example 1, preced- -ing, except that the dimaleate described under In other instances, however, such high boiling inert vaporizing solvent,

The same procedure is followed as in Com-,

assavoi COMPLETED Monoiumuc Diznrvsriivs Example 3 The same procedure is followed as in the two receding exam-pies, except that the trimaleate S substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED Monomnxro Dsnrvs'rrvs Example 4 The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the dimaleate,.or each pound mole of the 'trimaleate, instead of using one' pound mole of triricinolein, as a reactant, one

, jemploys two pound moles.

COMPLETED Monomrsrc DERIVATIVE Example 5.

The same procedure is followed as in Example 3, preceding,'except that for each pound mole ,of trimaleate, instead of adding one pound. mole of triricinolein, one adds three pound moles of triricinolein for reaction.

COMPLETED MoNoMnaIc DnarvA-nvn Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated glycerol (ratio 1 to has been employed as a raw material or primary reactant. In the present instance, a more highly oxyethylated glycerol is employed, to wit, one involving the ratio of l to 18. (See Oxyethylated glycerol maleate, Example 4, preceding.)

COMPLETED MONOMERIC Dmuvnrrvn Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerol employed represents one having an even higher degree of oxyethylation. For

example, one indicated by the ratio of 1 to 21.

(See Oxyethylated glycerol maleate, Example 5, preceding.)

CCMPLETED MoNoMmuc DERIVATIVE Example 8 The same procedure is followed as in Examples 1 to 7, preceding, except that succinic anhydride is'employed as a reactant instead'of maleic an h d i e COMPLETED MoNoMmuc DERIVATIVE Example 9 The same procedure is followed as in Examples played instead of maleic anhydride.

The method of producing such fractional esters is well known. The general procedure is to em ploy a temperature above the boiling point of water and below the pyrolytic point of the reactants. {The products are mixed and stirred March 30, 1937, to Frasier.)

.Sometimes esteriflcation is conducted most readily in the presence of an inert solvent, that "1' to 7, preceding, except that adipic acid is em- 1 carries away they water of esterification which.

may be formed, although as is readily 'appreciated, such water of esterification is absent when such type of reaction involves an acid' anhydride, such as maleic anhydride, and a glycol.

.However, if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry on the water formed. -The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. This is a conventional and well-known procedure and requires no further elaboration. In the previous monomeric examples there a definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact, that yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances where the by-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. In many cases when the compound is manufactured for purposes of demulsification, one is better ofi to obtain a polymer in the sense previously described, particularly a polymer whose molecularweight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose molecular weight is two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be removed before subsequent reaction. This, of

course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the effectiveness ofthe low multiple polymersas demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be vari ously replaced by substitucnts including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, nonhydroxylated amines, polyhydric alcohols, etc. Obviously, the

reverse is also true, in that a free hydroxyl group.

may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxy acetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that byproducts or cogeneric materials were formed, may be rccapitulated with. great definiteness, and one can readily appreciate that the formation of heat rearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be character- Although the products herein described vary so broadly in their'characteristics, i. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds, hydrotropic materials, balsams, subresinous materials, semiresinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation,

particularly the oxyethylation of the glycerol used as the raw material.

they may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one can not differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in waterin ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the obvious common property runningthrough the entire series, notwithstanding variation in molecular size and physical make-up, is absolutely apparent.v Such statement is an obvious oversimpliflcation of the rationale underlying demulsiflcation, and does not even consider the resistance of an interfacial film to crumbling, displacement, being forced into solu tion, altered wettability and the like. As to amidification polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

COMPLETED PoLYMERrc DEsrvArrvEs incwomc HEAT-REARRANGED COGENERS Example 1 One poundmole of oxyethylated glycerol dimaleate is reacted with one pound mole of triricinolein, with constant stirring, for a period of two'to 60 hours, at a temperature of 220-240 C., so as to eliminate sufilcient water in order to insure that the resultant product has a molecular weight approximately twice that of the monomeric material.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 2 The same procedure is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, or it may be a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

When employed as a demulsifier in the resolution of oil field emulsions,

deed, the formation of the monomer and poly I l COMPLETED POLYMERIC DERIVATIVES INcLunm g.

HEAT-REARRANGED Coosmms Example 3 The same procedure is followed as in Examples 1 and 2, preceding, except that chlorinate triricinolein is substituted in place of triricinolein COMPLETED POLYMERIC DERIVATIVES Iucumme HEAT-REARRANGED COGENERS Example 4 I The same procedure is followed as in Exa ples 1 to 3, preceding, except that one polymeri a mixture instead of a single monomer, for in stance, a mixture 'of materials of the kind described in Completed monomeric derivative, Ex ample 3, and in Completed monomeric derivativ Example 4, are mixed in molecular proportion an a subjected to polymerization in the manner indi cated in the previous examples.

It is understood, of course, that the polymeriz product need not be obtained as a result of :2 two-step procedure. In other words, one need not: convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step. In

merization may take place simultaneously.

is especially true if polymerization is conduc i in the absence of a liquid such as xylene, as pre viously described, and it one uses a compara tively higher temperature, for instance, approxi-; 'mately 220 C. for polymerization. Thus, orig;

pound mole of oxyethylated glycerol dimaleat of the kind described is reacted with one poun mole of tririeinolein for thirty hours at approxi mately 220 C. until the mass is either homoge neous or shows two separate layers, each of whic is homogeneous per se. It is stirred constant! during reaction. Polyfunctionality may reside dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be made in a single step illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greate or lesser degree, sufiicient monomeric materials so that a homogeneous system is present. subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibl an oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

' Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent. such as water; petroleum hydrocarbons such as gasoline, kerosene, stove oil;- a coal tar product mats, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and Jointly, and of the following formula:

CSHLOPKCQHJOLVHL [(cnmomo0011000121],-

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a water-insoluble completely esterified trihydric alcohol ester radical of which the acyl radicals are high molal hydroxy acid radicals having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11' represents the numerals 3 to 10; n: represents the numerals to 2; 3/ represents the numerals 0 to 2; and a represents the numerals 1 to 3. r I

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a. demulsifier comprising a polar member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and Jointly, and of the following formula:

iwmiowoocnoooz camohuclmownl" [(CaHaO)n 0 0 CRC 0 ORlL in which is a carboxyl-free radical of a dibaslc carboxy acid having not over 6 carbon atoms; R1 is a water-insoluble completely esterified trihydric alcohol ester radical of which the acyl. radicals are high molal hydroxy acid radicals having at least 8 and not more than 32 carbon atoms; Z

is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11 represents the numerals 3 to 10; 1: represents the numerals 0 to 2; 1/ represents the numerals 0 to 2 and z represents the numerals l to 3.

5. A process forbreaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler c,mo)..'ooonc 003,].

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a water-insoluble completely esterified trihydric alcohol ester radical of which the acyl radicals are high molal hydroxy acid radicals having at least Band not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; 1: represents the numerals 0 to 2; 1 represents the numerals 0 to 2; and z represents the numerals 1 to 3.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heatrearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a water-insoluble completely esterified triol ester radical in which the acyl radicals contain 18 carbon'atoms and at least one hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 12 represents the numerals 3 to l0;-:c represents the numerals 0 to 2; .11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

7; A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to' the action of a demulsifier comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heatrearranged derivatives of the monomers and aforementioned polymers, separately and jointly,

and of the following formula:

[(C2H4O)n'OOCRCOOZ],

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a triricinoleic radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 1/ represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

MELVIN DE GROOTE. BERNHARD mesa. 

